Nickel werner complexes of alphaarylalkylamines

ABSTRACT

The invention comprises a Werner complex of the general formula Ni(SCN)2Xn which is insoluble or sparingly soluble, in water at room temperature, wherein X is an alpha-arylalkylamine of the formula &lt;FORM:0994026/C2/1&gt; in which R1 is either hydrogen or a primary alkyl group and R2 is a phenyl radical carrying at least two further alkyl substituents in any of the 3-, 4- and 5-positions, and n is either 2 or 4. Preferably R1 contains 1 to 6 carbon atoms and the alkyl substituents of the phenyl radical have not more than two carbon atoms.  The complexes may be made, for example, by adding a solution of the arylalkylamine in heptane, or heptane-chloroform mixture, at room temperature to an aqueous solution obtained by dissolving NiCl2.6H2O and KSCN in water, and separating the resulting precipitate by filtration. The complexes may be used to form clathrates with aromatic compounds and the complex may be formed in the presence of the compound to be clathrated.  The clathrate may be formed by heating a complex Ni(SCN)2X4 with one or more clathratable compounds to a temperature sufficient to bring about complete dissociation of the complex into Ni(SCN)2X2 and free amine, and then cooling to effect recombination of the dissociated components to form a clathrate consisting of Ni(SCN)2X4 and the clathratable compound. The complexes of the formula Ni(SCN)2X4 may be used to resolve a mixture of aromatic organic compounds containing at least one clathratable compound by forming a clathrate, separating the clathrate from the mixture and dissociating the clathrate to recover the organic compounds. The clathrate may be dissociated by heating, by treatment with an acid which does not react with the clathrated compound, by steam stripping or treatment with an inert solvent. Clathratable compounds which may be extracted or resolved are, for instance, a ,a ,a -tri -fluorotoluene, nitrobenzene, nitrotoluenes, di-, chlorobenzenes, trichlorobenzenes, cresols, and benzonitrile. Novel amines which are suitable for complex formation are a -(3,4-dimethyl phenyl) ethylamine and corresponding butylamine and heptylamine; a  - (3,4,5 - trimethylphenyl) - ethylamine and - propylamine; a -(3,5 - dimethylphenyl) ethylamine and a -(3,4,5 - triethylphenyl) ethylamine.  They may be made by reductive amination of the corresponding ketone, for example by heating the ketone with ammonium formate.  Specifications 931,775, 935,099 and 945,012 are referred to.

United States Patent 3,177,234 NICKEL WERNER COMPLEXES 0F ALPHA- ARYLALKYLAMINES Pierre Marie Joseph Ghislain de Radzitzky dOstrowick and Jacques Daniel Victor Hanotier, Brussels, Belgium, assignors to Labofina, Brussels, Belgium No Drawing; Filed May 22, 1963, Ser. No. 282,231 Claims priority, application Great Britain, May 31, 1962, 2 1,098/ 62 26 Claims. (Cl. 260-439) This application is a continuation-in-part of application S.N. 183,318, filed February 26, 1962, now forfeited, which is a continuation-in-part of application S.N. 855,957, filed November 30, 1959, now abandoned, the latter application having claimed priority dates of December l, 1958, for British application 38,654 and October 7, 1959, for British application 33,987.

The present invention relates to new chemical complexes and more particularly to chemical complexes which are only slightly soluble or insoluble in water at room temperature, these complexes being of the Werner complex" type.

It is an object of thepresent invention to provide new chemical complexes'of the Werner type.

It is another object of the present invention to provide new chemical complexes which can be used for the refining or the resolution of very closely related organic compounds into their individual components.

It is also an object of the present inventionto provide for the production of the new chemical complexes of this invention.

Other aspects and advantages of the present invention will be apparent from a further reading of the specification and of the appended claims.

For the purpose of simplicity the novel compounds of this invention will be described in two sections, the first section being directed to nickel complexes of unsubstituted and monosubstituted phenylalkylamines, and the second section being directed to nickel complexes of polysubstituted phenylalkylamines.

UNSUBSTITUTED AND MONOSUBSTITUTED PHENYLAKYLAMINES According to the present invention, there is provided a Werner complex of the general formula Ni(SCN) X wherein n is either 2 or 4, X is an arylalkylamine of general formula H- I NH in which R is either hydrogen or a primary alkyl group,

R is an hydrocarbon radical having one benzenic ring,

.said benzenic nucleus bearing no more than one alkyl ice Even more preferably the group R; will have no more than 3 carbon atoms and R no more than 9 carbon atoms. When the benzenic ring of R is substituted with an alkyl chain this substitution is preferably in the parap-Methylbenzylamine po 113- cam-o Hr-NH, p-Hexylb enzylamine p- C ,H13-o,H,-oHz-NH, u-Phenylethylamine o UHF o H- 0 H I'm. a-Phenylpropylamine 0 0H,- 0H 0,13 1 :11, u-Phenylbutylamine o H -CH- C3H1 l lfiz u-Phenylamylamine 0 ,m- 0 H- 0 11 I'm. u-Phenylisoamylamine oan -on-om-onwrn i111, a-Phenylhexylamine CaH|s-0H- 5 u I IH,

a-Phenylisohexylamine CBH5-CH(CHI)Q-CH(OHB)1 a-Phenylheptylamine or-(p Toly1)ethy1amine p-CH -C H OH-CH;

oc- (p Ethylphenyl) ethylamine p-C,H -CaBI4-CHCH;;

a-(p-CumyDethylamine oHa ,oB:-com-orr orr,

11TH: a-(p-Ter-butylphenyl)ethylamine IJ-( e)aCCaH4CH-CH a- (p-Hexylphenyl) ethylaminepC H1 GsH4CHCH u(p-Nony1phenyl) ethylarnine D' nH1sCsH4-CH-CH a-(o-Tolyl)propylamine i o-CH C H 0H-, O ,H,

a-(p-TolyDbutylamine p-CH -CQH CHC H u-(p-CumyDbutylamine i GHmOH-Qmr-CH-QH,

a-(p-TolyDheptylamine D-CHQ"-COH4'-CH-COH13 ILIH:

oz- (p-Propylphenyl) decylamine p-C H C H4CH,CuHm

1 1 2 a-(p-Nonylphenyl)butylamine.

p-C9H1oCaH4CH-C H All of the hereinabove described amines have no, or only a slight ammoniacal odor. They thus differ markedly from heterocyclic nitrogen bases which have strong and persistent nauseating odors.

. All of the above described amines also havea low toxicity compared to the nitrogen heterocyclic bases such as pyridine bases.

The complexes thus defined are insoluble. in water and when the amino group is not on the carbon adjacent to In order to get a satisfactory complex for clathration it is necessary to limit the number of alkyl carbon atoms in at least one of the 2 radicals R or R to a maximum value of 3, preferentially 1, the total number of carbon atoms of R and R being respectively not over 9 and 15.

Above these limits'the complexes get a sticky appearance and get more and more soluble in aromatic hydrocarbons. e n n n p The use ofsuch compoundsin clathration is, of course, either impossible or unattractive.

It has been found also that steric effect might impede the formation of clathrates. or even of the complex.

Such exceptions have been met. for the benzylamine andalso when the radical R is not a primary one, by example in the amine:

Ri-CH-JDH 1 NH: 113' n I It will be noted, that the same jlimitation is met thebenzenic radical.

The amines having no more than 3 carbon atoms in R and 9 carbon atoms in R are'more advantageous because of the larger availability of intermediates for the synthesis of said amines.

The amines having an. alkyl'substituent in the meta or ortho position are less. advantageous. They are more difiicult to synthesize and the complexes made with those amines react less easily in clathrating processes. 1

It is alsoto be noted that no choice is made regarding the. form of the'anion'SCN. This formula must beitaken as a whole and not restricted specifically to any of the normal or iso form.

The replacement of SCN by SeCNfgivescomplexes having approximately the samegeneral properties. Nevertheless these complexes are much. less attractive than SCN because of their slight availability.

The clathrating activities of the: complexes are not only very sensitive to the structure of the amine but also to the nature of the other components. of the complex.

Experience. has shown by example that cobaltous and cyano complexes. with theiherebefore described amines in aliphatic hydrocarbons at ordinarytemperature. They are generally soluble in organic polar solvents.

These complexes can be dissolvedin organic polar solvents thus permitting the introduction of the nickel into a solution which could be used for impregnating catalytic masses. In solid form they can also be used in heterogeneous catalysis.

Those complexes have also a wide field of application as clathrating agents for the .selective extraction of aromaticv compounds.

When used as clathrating agents, the Werner-complexes hereinabove 'defined must not dissolve to a large extent aromatic hydrocarbons at.v work temperature.

Itv has been found that this solubility is bound to the number of alkyl carbon atoms. in R and R do not show the samefclathrating activities as the claimed composition.

Those clathrating properties are quite unexpected if one considerslthatbeta isomers of the hereabove described amines give non-clathrating complexes, and also that the benzylamine,.the inferior homolog of the hereabove described aminesgives complexes having no clathrating activities.

The'new complexes themselves are quite unexpected if one considers that such complexes are not obtained,

With other components such as Ni, SCN, N-methylaniline Ni, SCN, N-butylaniline Ni, SCN, NN'dimethylaniline, F e, SCN 'benzylamine As clathrating. agents they permit 'theextracting'of,

certain'organiccompounds and the resolving of certain organic'mixtures. V 1

It has. so been possible to. extract methylnaphthalenes from a coal tar fraction using complexes following the invention,

' Resolving of mixtures will be described withreferen ce to specificcasesas hereinafterdescribed.

1 7 Of the cymene isomers only-pcymene maybe obtained commercially inthe pure form. For some applications o cymene is. suitable blItQWasxup .to now verydiflicult' to obtain inrthe, .pure: forrng Neither isomeriizationiof. 7

p-cymene by aluminum chloride, nor allrylationv oftolu- ,ene'in the presenceof AlCl gives 'a yield. above 5% in the ortho isomer. Nevertheless, it is possible to get a yield of about 40% of the ortho isomer by reacting toluene and isopropanol in the presence of chlorosulfonic acid. As the boiling points of cymene isomers are very close 175, 1 C.; m-, 175, 6 C.; p-, 17 6, 9 C.) distillation cannot achieve their separation. The ortho isomer may be easily separated out of the crude mixture obtained by the last synthesis outlined above, using clathration by one of the complexes conforming to our general definition.

For clathrat-ing such a synthesis efiiuent by [N i(SCN) (alpha-phenylethylamine) a solution of 0.0784 mole o alpha phenylethylamine in 30 m1. of the mixture of cymenes (in mole percent: 0-, 41; m-, 21; p-, 38) is slowly added, while stirring at room temperature, to an aqueous solution obtained by dissolving 0.01 85 mole of NiCl .6H 0 and 0.0370 mole of KSCN in 20 ml. distilled water. After stirring for 15 minutes, the resulting precipitate is then separated by filtration, washed three times in 50 ml. of pentane and dried in air. 10 g. of the dry precipitate are decomposed by 40 ml. of 6 N HCl.

The supernatant organic phase is recovered and analyzed by infra-red spectroscopy. It is thus found that 10.8% of the solid obtained are essentially o-cymene (in mole percent: o-, 92; m-, 7; p-, 1). The remainder is formed essentially by the complex [Ni(SON) (amine) as shown by analysis of each constituent,

For clathrating a mixture of p-cymene and methylnaphthalene by [-Ni(SON) (alphaaphenylbutylamine) a solution of 0.0401 mole of alpha-phenylbutylamine in 25 ml. of an equimolar mixture of p-cymene and commercial methyl-naphthalene (Grade No. 1 A.S.T.M. alpha-methylnaphthalene) is added, while stirring at room temperature to an aqueous solution obtained by dissolving 0.0093 mole of NiCl .6H O and 0.01 85 mole of KSCN in 10 ml. of distilled water. Atter stirring for 15 minutes, the resulting precipitate is then separated by filtration, washed three times in 30 ml. of pentane and dried in air. gr. of thedry precipitate are decomposed by ml. of 6 N HCl.

The supernatant organic phase is recovered and analyzed by vapor phase chromatography. It is thus found that 9.1% of the solid obtained are essentially methylnaphthalene (methylnaphthalene, 98 mole percent; p-cy mene, 2 mole percent). The remainder is formed essentially by the complex ['Ni(SCN) (amine) For clathrating a mixture of p-xylene and p-cymene by {Ni(SON) {alpha-(ortho-tolyl)ethylamine} a solution of 0.0281 mole of alpha-(ortho-tolyl)ethylamine in 17 ml. of an equimolar mixture of p-xylene and p-cymene is slowly added, while stirring at the ice bath temperature, to an aqueous solution obtained by dissolving 0.0062 mole of NiCl .6H O and 0.0124 mole of KSCN in 7 ml. of distilled water. After stirring for minutes, the resulting precipitate is then separated by filtration, washed twice at the ice bath temperature by 20 ml. of pentane and dried in air. 4 gr. oi the dry precipitate are decornposed by 10 ml. of 6 N H01. The supernatant organic phase is extracted by 2 ml. of heptane and analyzed by vapor phase chromatography. -It is thus found that 8.9% of the solid obtained are essentially p-xylene (p-xylene, 94 mole percent; p-cymene, 6 mole percent). The remainder is formed essentially by the complex zt n 4] and 0.0185 mole of KSON in 10 ml. of distilled water. After stirring for 20 minutes, the resulting precipitate is then separated by filtration, washed three times at the ice bath temperature by 50 ml. of pentane and dried in air. 5 gr. of the dry precipitate are decomposed by 10 ml. of 6 NHOI. The supernatant organic phase is extracted by 3 ml. of pcymene and analyzed by vapor phase chromatography. It is thus found that 14.5% of the solid obtained are aromatic hydrocarbons (met-hylnaphthalene, 88 mole percent; o-xylene, 12 mole percent). The remainder is formed essentially by the complex 'Ni (SC-N) (amine) 'ethylamine in 25 ml. of an equimolar mixture of p-cymono and commercial methylnaphthalene (Grade No. 1 A.S.T.=M. alpha-methylnaphthalene) is slowly added, while stirring at room temperature, to an aqueous solution obtained by dissolving 0.0093 mole of NiC1 .6H O and 0.0185 mole of KSCN in 10 ml. of distilled Water. After stirring for 15 minutes, the resulting precipitate is separated by filtration, Washed three times in 30 m1. of pentane and dried in air. 5 gr. of the dry precipitate are decomposed by 10 ml. of 6 N HCl. The supernatant organic phase is recovered and analyzed by vapor phase chromatography. It is thus found that 13.1% of the solid obtained are essentially methylna'phthalene (methylnaphthalene, 9 3 mole percent; p-cymene, 7 mole percent). The remainder is essentially the complex [Ni(SON) (amine) Crude mixtures of monomethylnaphthalenes are obtained by distillation of coal tear or from an aromatic petroleum traction. Mixtures of monomethylnaphthalenes are used as such, e. g., as reference fuel inthe A.S.T.M. method. For some other uses, like further synthesis, one may want one of the two isomers in the pure form. The ,B-isomer is obtained in a pure form by freezing it out of :the mixture. The a-isomer is more difiicult to get in the pure form. Clathra-tion of such a mixture by one of the complexes conforming to our general'definition leads to the separation of the a-isomer.

For clathrating an isomer mixture of methylnaphthala solution of 0.0425 mole of alpha- (para-cumyD-ethylamine in 25 ml. of a commercial methy-lnaphthalene (Grade No. I A.S.T.M. ialpha-methylnaphthalene containing 52% of the a-isomer, 42% of the fl-isomer and 6% indole) is slowly added, while stirring at the ice bath temperature, to an aqueous solution obtained by dissolving 0.0093 mole of NiC1 .6H O and 0.0 mole of KSON in 10 ml. of distilled water. After stirring for 30 minutes, 75 ml. iced pentane are added for speeding the crystallization of the complex. The resulting precipitate isfseparated by filtration, washed three times in 30 ml. of pentane and dried in air. 5 g. of the dry precipitate are decomposed by 10 ml. of 6 N HCl. The supernatant organic phase is extracted in 3 ml. of p-cymemo, and analyzed by vapor phase chromatography. It is thus found that 18.7% of the solid obtained is chiefly alpha-methylnaphthalene (oz-isomer, 83%; fi-isomer, 17%). The remainder is essentially the complex In another set of experiments, this commercial methylnaphthalene has been acid washed in order to eliminate complexes of the type R1 l (S ON) 2 I 2) 4] Amine Composition of p methylnaphthalenes in weight percent Selec- No. in the clathrate O tivity Feed: a= 55 fl= 45 1 p-OHaCaH4 84 16 14. 1 a 9 GIFT 71 29 22. 2 a 2 CRT-Tr 23 77 26. 5 8 4 CRHR 24 76 16. 3 6 i CARR 56 44 13. 2 a 6 Cnfir 65 35 20. 2 a 7 CAHK 17 83 13. 1 B 3 CA; 31 69 13. g 9 C5115 71 29 6. 9 oz 64 36 20.0 a

IJ-CH -CbHt 63 37 19. 6 a

pCHa-CsH4- 71 19 6. 9 a

O *=Weight of clathrated methylnaphthalenes/W eight of olathtateXlOO. For separating a mixture of Xylenes, a solution of the dry elathrate are decomposed by 40 ml. of 20% stoichiometric quantity) of alphaaphenylisohexylamine in 50 ml. of an equimolar mixture of the threezxylenes is slowly added, while stirring at the bath temperature,

7 14.67 gr. (82.7 mM., that is to say a 12% excess over the H 50 The supernatant organic phase is. recovered and analyzedby infra-red spectroscopy.

Similar tests'made'with complexes of otheramines have given the results mentioned in Table II.

Table II.Clafhration of xylenes using comple ses of the type 7 R1 I )B{ I 2}4I Amine Composition of Xylene (Weight Percent) iiiv N0. 1 a C Selec- Feed Clothrate tivity R1 R2 o m p om p 1. CF!- CRFYK 37 31 32 62 19 V 19 18. 2 o 9 C 111; CHI; 37 31 32 12 26 92 17. 8 p 2 CRT'TI (nFl's 37 31 32 23 7 70 11.3 p 4 CAHG CAP 34 31v 84 13 a 3 10.8 0 5- i-CAHQ 07H 34 32 34 72 2O 8 17.5 0 6 CsHu CsHs 34 32' r 34 5 71 24 8.9 m 7- l-CfiHv CaHa" V 35 31 34 13 76 11 9.8 In 8 aH1s .CcHs 34 32 34 12 v -80 8 8.9 m 9 C H CaHs 35 32 33 26 62 a 12 9.9 In 10 C H CAHK V 35 32 33 17 61 22 10. 1 m 11 C0H1s CeHs 35. 31 34 86 11 3 5.4 o

CuHs 34 32 v 34 22 71 7 1.6 m .O-CHr-CoHn: 0 48 52 0 10 9D 6. 0 p

. 0 50 17 0 83 4.1 Q-CHae-CaH; 34 3O 36 11 29v 13.8 0 P-C Hs -Cgfil; 37 31 32 78 18 4 9. 3 o p-(CHa)zCH-'COH4 .e 37 31 32 89 8 I 3 12.3 0 V romote-0am 37 31 32 83 13 4 6. 8 0

p-C9H19-CsH4 34. 32- 34 9 31 60 5. 5 p p-OHa'O Hi 34 32 34 58 31' r 11' 8.9 o p-OH3OH4 341 32 34 33 '56 y 11 8:3 in I O *=Weight of clathrated xylenes/Weight of clathrate X100;

to an aqueous solution obtained by dissolving 4.40 gr. (18.50 mM.) of NiCl .6H O and 3.70 gr. (38.10 rnM.)

of KSCN in 10 ml. of distilled water. After stirring for 20 minutes, the precipitate which is obtainedis filtered offitand washed twice: the first time by stirring in ml;

of heptane and the second time in 70 ml. of pentane. The

precipitate is finally filtered 01f againand dried in a thin layer at room ipressure and temperature for 30 minutes.

The resulting clathrate is a blue powder composed of Xylene and of the complex conforming tot-he general formula [N:i(NCS) '(aInine) as shown bythe analysis:

arnine/'Ni= 3.99 are very olose to the theoretical values 2 and 4. For analyzingthe clathratedixylenes, 5 g. of

the-molar ratio ,amine/=NCS=2.02 and the molar ratio 1 plex being obtained :by displacement of theequilibrium.

For example;

Niclg gzKcns zimxeaminq-snuscm xgzno It has, on the other handybeen found that-the cornpleXes prepared in aqueous medium always contain more or less large quantities off-hydroxide .of 'th'e ba's'e; metal which is thusdepriyed iofrits active function; V

In order to avoid this formation of hydroxide it is obviously possible to operate in the absence of Water, for example by causing the amine to react, in vapor form with, the solid salt.

Such procedure is obviously slower and more ditficult to carry out than the liquid phase procedure referred to above.

It has been found possible to combine the advantages of working in liquid phase and the elimination of nickel hydroxide formation in adding to the aqueous phase a non-aromatic hydrocarbon in quantity sufficient to impregnate the complex (which itself is lipophilic), for example by using a solvent quantity of 1/1 by weight with respect to the complex to be formed.

In this way there are obtained complexes almost free of nickel hydroxide. Surprisingly this process has also beneficial effect on the crystallization velocity and the ease of settling.

The hydrocarbon is chosen so as not to interfere with the operational process and so as to be easily removed after the complex is prepared.

The following examples illustrate what has been said above for the compositions of the complexes as well as their preparation and their properties.

EXAMPLE 1.-PREPARATION OF [Ni(NCS)2(a-PHENYLAMYLAMINE)4] A solution of 13.50 gr. (82.70 mM., that is to say a 12% excess over the stoichiometric quantity) of a-phenylamylamine in ml. of heptane is slowly added, while stirring at room temperature, to a binary mixture comprising 10 ml. of heptane and an aqueous solution obtained by dissolving 4.40 gr. (18.50 mM.) of NiCl .6H O and 3.70 gr. (38.10 mM.) of KSCN in 10 ml. of distilled water. After stirring for minutes, the precipitate which is obtained is filtered OE and washed by stirring in a mixture of 20 ml. of heptane and 10 ml. of water. This washing removes any remaining salt or unreacted amine. This precipitate is filtered off again and dried in a thin layer under vacuum at room temperature for two hours. The resulting complex is a blue powder conforming to the formula [Ni(NCS) (amine) as shown by the analv ysis (see Table II).

EXAMPLE 2.-PREPARATION OF [Ni SCN 2 a-PHENYLNONYLAMINE 4].

16.23 gr. (74.0 mM.) of u-phenylnonylamine are slowly added, while stirring at the ice bath temperature, to an aqueous solution obtained by dissolving 4.40 gr. (18.50 mM.) of NiCl .6H O and 3.70 gr. (38.10 mM.) of KSCN in ml. of distilled water. After stirring for 30 minutes, the precipitate which is obtained is filtered oif and washed by stirring in 50 ml. of distilled water. The precipitate is filtered off again and dried in a thin layer under vacuum at room temperature for two hours. The resulting complex is a blue powder conforming to the formula [Ni(NCS) (amine) as shown by the analysis (see Table H).

EXAMPLE 3.PREPARATION OF [Ni (NCS 2 (aPHENYLO CTADECYLAMINE) 4.]

25.57 gr. 74.0 mM.) of a-phenyloctadecylamine are slowly added, while stirring at room temperature, to an aqueous solution obtained by dissolving 3.23 .gr. (18.5 mM.) of Ni(NCS) in ml. of distilled water. After stirring for 30 minutes, the precipitate which is obtained aqueous solution obtained by dissolving 4.40 gr. (18.5 mM.) of NiCl .6I-l O and 3.70 gr. of KSCN in 30 ml. of distilled water. When stirring for 30 minutes, 3 ml. of heptane are added for improving the crystallization of the complex; then the precipitate is filtered off and washed by stirring in 50 ml. of distilled water. The precipitate is filtered off again and dried in a thin layer under vacuum for two hours. The resulting complex is a blue powder conforming to the formula [Ni(NCS) (amine) as shown by the analysis (see Table III).

EXAMPLE 5.PREPARATION OF [Ni NCS 2{a. (1J NONYLPHENYL) -ETHYLAMINE}4] 18.31 gr. (74.0 mM.) of ot-(p-nonylphenyl)ethylamine are slowly added, while stirring at the ice bath temperature, to an aqueous solution obtained by dissolving 4.40 gr. (18.50 mM.) of NiCl ol-l o and 3.70 gr. (38.10 mM.) of KSCN in 40 ml. of distilled water. After stirring for 30 minutes, the precipitate which is obtained is filtered off and washed by stirring in ml. of distilled water. The precipitate which is obtained is filtered off again and dried in a thin layer under vacuum at room temperature for 15 hours. The resulting complex is a blue powder conforming to the formula [Ni(NCS) (amine) l as shown by the analysis (see Table III).

EXAMPLE 6.PREPARATION OF [Ni(NCS)2{a-(p-TOLYL)HEPTYLAMINEh] 15.20 gr. (74.0 mM.) of a-(p-tolyl)heptylamine are slowly added, while stirring at the ice bath temperature to an aqueous solution obtained by dissolving 4.40 gr. (18.5 mM.) of Nichol-I 0 and 3.70 gr. (38.10 mM.) of KSCN in 40 m1. of distilled water. After stirring for 20 minutes, the precipitate which is obtained is filtered off and washed by stirring in 70 ml. of distilled water. The precipitate is filtered off again and dried in a thin layer under vacuum at room temperature for 3 hours. The resulting complex is a blue powder conforming to the formula [Ni(NCS) (amine) as shown by the analysis (see Table III).

PREPARATION OF THE TWO-BASE COMPLEXES The two-base complexes conforming to the formula [Ni(NCS) (amin6) are prepared by the same procedure as the corresponding four base complexes except for the following differences:

EXAMPLE 7.-PREPARATION OF [Ni (NCS 2{CL- (p-TER-BUTYLPHENYL ETHYLAMINE}2] A solution of 6.55 gr. (37.0 mM.) of a-(p-ter-butylphenyl)ethylamine in 5 ml. of chloroform is slowly added, while stirring at the ice bath temperature, to a binary mixture comprising 25 ml. of heptane and an aqueous solution obtained by dissolving 4.40 gr. (18.5 mM.) of

NiCl .6H O and 3.70 gr. (38.10 mM.) of KSCN in 10 ml.'of distilled water.

After stirring for 30 minutes, the precipitate which is obtained isfiltered ofiand washed twice: the first time by stirring in a mixture of 30 n11. of heptane and 10 ml. of distilled-water and the second time in 60 ml. of chloroform. The precipitate is finally filtered off again and dried in a thin layer under vacuum at 45 C. for 2 hours. The resulting complex is a green powder conforming to the l I" formula [Ni(NCS) (an1ine) as shown by the analysis (see Table III).

The color and the ratio X/NCS-X/Ni of series of complexes prepared following the process indicated in the 12 insoluble or slightly soluble complexes in aromatic hydrocarbons at room temperature.

It is thus preferred that there be 1 to about;6 carbon atoms in the R alkyl'g'roup, even more preferably .1 to

[Ni (N C S) 2 (p methylb enzylamine) 4] Ni (N C S) z(a-phenylethylamine)i Ni (N C S) r (a-phenylethylamine) 2]. N i (NC S) z(a-phenylpropylamine) i Ni (N C S) z(a-phenylisoamylamiue) z] N i(NCS)gm-phenylhexylamine) 4] Ni (N OS)g(a-phenylhexylamine) 2] N i(NOS) (a-phenylisohexylamine) 4] Ni(N CS) 2(wphenylheptylamine) I N i(NCS)z(a-phenylheptylaminei z] Ni(N C S) 2(a-phenyloctylamine); Ni(N GS)z(a-phenyloetylamine)2]-.

N i(NOS) (a-pheny1n0nylamine)4] Ni(N CS)z(a-phenylnonylamime)z] N i(N C S) 2 (vr-phenyldecylamine) Blu N1(N CS) (a-phenyloctadecylamine) i] r N i(N CS); i a-(o-tolybethylamine )4] Ni(NGS)2 a(m'-t0lyl)ethylamine)4] N i (N CS) 2 a-(m-tolyl) ethylarnine 2] N1 902 a-(p-tolyhethylamine Bl N i (N OS); a-(p-tolybethylamine 2] amine 4 Ni(NGSM a-(pcumyl) ethylamine h Ni(NCSni a-(p-cumyhethylamine z] Ni(NOS)z a-(p-ter-butylphenyl) et yl- [Ni(NOS); a-(p-tolybheptylaminezl [Ni(NO S) A 01- (p-nonylphenyl) butylamine i4] [Ni(NC S) gl a-(p-propylphenyl) nonyl- V armne 2 [Ni (NC S) 24 a-(p-propylphenyl)nonylamine h] Blue Blue

Pale green Blue POLYSUBSTITUTED PHENYLALKYLAMINES According to this aspect of the invention, there is provided a Werner complex of the general formula Ni(SCN) X which is insoluble or sparingly soluble in water at room temperature wherein X is an alpha-arylalkylaminei having the general formula: v

'less a probability of getting steric effect impeding the formation of the complex will be met with the higher alkyl'groups, also" the solubility and'the physical aspect of the complex depend on the length of the chain R and,

the complex will get lessand less insoluble in hydrocarbons and-more and more waxy as thelength "of the-chain-Ri increases; t

7 When used as clathrating agents, the Werner complexes 7 here defined must remain solid and not dissolve. to a large p extent in'aromatic compounds to be cl'at-hrated. 'A pre ferred embodiment of this invention will: so comprehend For similar reasons the preferred alkyl= substituents of R will be; either methyl or ethyl; groups, that is to say the alkyl substituents'of the phenyl radical preferably have not more than 2 carbon -atoms.- a

All substituents of R will also be conveniently identical in one compound. p

Substitutionin 2 or 6 position is less suitable for forming complexes where n is 4. Such complexes when they are obtainedare also less active clathrating agents.

Most preferably there will be 2 methyl substituents in positions 3 and 4.

Specific but not limitative examples of the hereinbefore described class of arninated bases are:

IM.P.

a-(3,4,5-trimethylphenyl)propylamine.

a B.P.,

O./mm. Salt), C.

a-(3,4-dlrnethylphenyl)butylamine 271-2 1.5156

NHz

a-(3,5-dimethylpl1enyl)ethylamine NHn H- C-GHa NHz l CH3 CH CH3 a-(3,4,5-triethy1phenyl)ethylamine H-G-CHa Cr a All amines hereabove described have little or no ammoniacal odor, thus differing markedly from heterocyclic nitrogen bases, which exhibit strong and persistent nauseous smelling. In addition, all amines hereinbefore described have a very low vapor pressure, thus reducing fire risks.

. 14 heating the ketone with ammonium formate (Leuckart reaction).

It is to be noted that no choice is made regarding the form of the anion SCN. The formula SCN must be taken as a whole and not be restricted specifically to any of the normal or iso forms. Replacement of SCN by SeCN gives also complexes having approximately the same general properties. Nevertheless these complexes are much less attractive because they are not readily available as compared to the SCN complexes.

The complexes have numerous uses: they can be dissolved in organic polar solvents, thus permitting the introduction of nickel into these solutions, in which it can act as oxidation or polymerization catalyst. They can also be used in solution for impregnating catalytic masses.

' In solid form they can be used as heterogenous catalyst or as clathrating agent.

As clathrating agents, they permit resolution of mixtures which are difficult to resolve by conventional methods, particularly mixtures of aromatic isomers.

In such uses they show unexpected properties. By example, for the separation of polar substituted aromatic compounds. As is shown by the specific examples given hereafter, the complexes exhibit high selectivities and good capacities towards aromatic molecules carrying at least one polar group such as an halogen, a nitro, a cyano,

or even a hydroxyl group. Such compounds were either difiicult or impossible to separate with previously described complexes of the Werner type. They form therefore a convenient means for resolution of mixtures of isomers of polar aromatic compounds.

When compared with complexes of the same general formula but using other types of arylalkylarnines, the complexes of this invention exhibit a marked and highly unexpected superiority in such separation processes.

The preparation of the complexes according to the in-' vention will now be described with reference to the following non-limitative example.

EXAMPLE 8.PREPARATION OF [Ni SCN 2{a- (3,4-DIMETHYLPHENYL) ETHYLAMINE}4] A solution of 0.0250 mole of a-(3,4-dimethylphenyl) ethylamine in 6 ml. of heptane is slowly added, while stirring at room temperature, to an aqueous solution obtained by dissolving 0.0056 mole of NiCl -6H O and 0.014 mole of KSCN in 6 ml. of distilled water. After stirring for 30 minutes, the resulting precipitate is then separated by filtration, washed with a mixture of 6 ml. of heptane and 6 ml. of water and dried for 2 hours under vacuum at room temperature.

The composition of the resulting 4-base complex is shown in Table IV.

The other complexes in accordance with the invention are prepared in a similar manner.

The two-base complexes are obtained by using stoichiometric quantities of reactants, i.e., 2x moles of amine, x moles of NiC1 -6H O, 2x moles of KCNS, a slight deficit of amine being advisable. Furthermore, the 2- base complexes are easier to obtain in a pure form when an equal quantity of chloroform is added to heptane either for the formation and for the washing of the complex; those complexes are then dried for 2 hours under vacuum at C.

For complexes conforming to the general formula Ni(SCN) X the theoretical values of the molar ratio SCN/Ni and X/Ni are respectively 2 and 4 when n is 4, and 2 when n is 2.

'For the complexes hereinabove described, we have found, by functional analysis, ratios very close to the theoretical values leaving no doubt about the composition of thecomplexes.

The solubility of the new complexes in methanol has been determined. This solubility may be increased by adding to the methanol some of the corresponding amine.

Table l V Complexes Color Molar ratios Solubility in Methanol X/Ni SON/Ni [N1(S CN)gioi-(3,4-dimethylphenyl)ethyl- 4. 34 2.00 Very soluble. [lig sf fii ta-(3,4-dlinethylphenyl)buty1- 3. 96 1. 96 Soluble. lb zg Ni iid (3,4-dlmethylphenyllheptyl- 3. 98 i 97 Very soluble. ll i fggNii{a-(S;5-dimethylphenyl)ethyl- 3. 96 1. 99 'Slightly soluble. [I ?i S N )iiLit-(3A,5-trimethylphenyl)ethyl- 4. 25 2.01 Very slightly soluble. [Ni f C l lhid (3,4,5-triethylphenyl) ethyl- Blue 3. 96 1. 96 Soluble. ll g s g bla iia-(3;4,5-trin1ethylphenyl)propyl- -do 4. 02 1. 94 Slightly soluble. [$233 Naila-(3,4-dlmethylphenyl)ethyl- Green 1. 92 1. 95 D0. [I I i S% l I )ila-(3,4,5-trimethylphenyl)ethyl- Pale green 2.07 I 2. 04 Very slightly soluble; [$23616 51.1- (3,4-dimethylpheny1)heptyl- 2. 09 2. 02 Soluble. amino) 2]. V

The new. complexes are particularly useful as clathrating agents for the extraction or the separation of isomers of aromatic molecules. In such process they prove to be particularly effective for extraction or refining-of polar aromatic compounds. T

Such'molecules which may be extracted or resolved intotheirisomers by clathrationwith the new complexes are for instance:

, This list isby no means limitative and many other aromatics such as xylenes and methylnaphthalenes are 7 also clathrated. 7

Complete recovery by crystallization of one isomer-out.

of a crude mixture is often limited by the formation of an eutectic or by the precipitation of mixed crystals:.

clathration often permits a much better recovery of the product beyond those concentration limits.

methylphenyl)ethylamineh] a solution of. 0.0 250 mole of a-(3,4-dimethylphenyl)ethylarnine in 12 m1. of,a mixture comprising 9 ml. of dichlorobenzenes and 3 ml. of heptane is slowly added, while stirring .at the icebath temperature, to an aqueous solution obtained by dissolving 0.0056 mole of NiCl .6H O and 0.0114 mole of KSCN in 6 ml. of distilled water. Afterstirring for -30' minutes, the resulting precipitate is then separated by filtration, washed once with 20 m1. of heptane and once with 20 ml. of pentane and then dried in air. I r p 3 g. of the dry precipitate-are decomposed by 10 ml. of 20% sulfuric acid. After decomposition; the sulfuric acid is diluted by 20 ml. of distilled water andthe clatha found that 15.7% of the solid obtained consistsof di- For instance,

separation of dichlorobenzenerisomers by clathration with the-new Werner complexes willbe described with reference to the following specific case.

For clathratingamixture of dichlorobenzenes (in'molepercent o-; .33; m-; 33; p-; 34') by [Ni(SCN) {a-(3,4-dichlorobenzene isomers with astrong enrichment of the para-isomer (in mole percent; 0}, 3; m-; 4; p-, 93).

The remainder consists essentially of the complex )2( )4l- V a Other resolutions of mixtures. of aromatic. compounds are realized by the same procedure'employing the same complex or the, othercomplexes according to the invention; the results of such clathrations are summarizedtogether with the preceding results inTable V.

Table V Composition of Clathrated Composition of the feed the elathrated compounds in Amiuated base of the Lbase complex (moles percent) mixture (moles the clathrate percent) (weight percent) a(3;4-dimethylphenyl)ethylamine Dichlorobenzenesz I 93 a-(3,5-dimethylphenyl) ethylamine 35 7 7 a-(3,4,5-trimethylphenyl) ethylamiue 39 5 1 1 so 35 10.1 35 p: 35 30 Toluene: 51 23' Benzotrifluorlde: 49 77 ,8.5 a-(3A dimethylphenyl) butylamlne Dichlorobenzenes: 36 8 9 23 Di $1348"-.. 41. en enes: a (3,4,5 triothylphenyl) ethylannne V 070353;? n '40 v 12.1

'p:34 "32 Nltrotoluene p:; 31' Toluene: 43' I Benzotrlfluo rated dichlorobenzenes are extracted by 10 ml. of cyclo-- in which Table V-Continued Aminated base of the l pase complex Composition of the feed I (moles percent) a-(3,4-dlmethylphenyl) butylamine Trichlogobgnzenes:

. l 4 1,2,4: 51 a-(3A-dimethylphenyl) heptylarnine Chloroggluenes: I o:

p 34 a-(3,4,5-trimethylphenyl)propylamine Composition of Clathrated the clathrated compounds in mixture (moles the clathrate percent) (Weight percent) properly, equitably, and intended to be, within the full range of equivalence of the following claims.

What is claimed is:

1. A -Werner complex having the general formula Ni(SC N) X, wherein n is an even number from 1 to 5, X is an alpha-arylalkylamine having the general formula H--NHz R isselected from the group consisting of hydrogen and primary alkyl radicals containing from one to nine carbon atoms, R is an hydrocarbonradical containing from six to fifteen carbon atoms, said radical having one benzenic ring, said benzenicring being directly linked to the carbon atom bearingithe amino group, the total number of carbon atoms of the amine being greater than seven. v

2. A Werner complex having the general formula Ni(SCN) X, wherein n is an even number from 1 to 5,

Ni(SCN) X,, wherein n is an even number from 1 to 5, X' is an alpha-arylalkylamine having the general formula R1 n-{J-NH) I R2 in which v R is selected from the group consisting of hydrogen and primay alkyl groups having from 1 to .9 carbon atoms,

' X is an alpha-arylalkylamine having the general formula R is a phenyl radical substituted by one alkyl radical having from oneto 9 carbon atoms, at least one of the radicals R and R containing not more. than 3 alkyl carbon atoms. v V

4. A Werner complex having the general formula 1 Ni(SCN) X wherein n is an even number from 1 to 5,

X is an alpha-arylalkylamine having the general formula R1 H-+-NH2 in which R is selected from the group consisting of hydrogen and primary alkyl groups having from 1 to 9 carbon atoms,

R selected from the group consisting ofdi-alkyl and tri-alkyl-substituted phenyl radicals wherein substitution occurs at any of the 3, 4 and 5 portions of said phenyl radical, said alkyl substituents each having less than 3 carbon atoms.

5. A complex selected from the group consisting of:

[Ni(NCS (p-methylbenzy1tamine) [Ni (NCS ot-phenylethyl amine) [Ni NCS (a-pheny1ethylamine [Ni (NCS 2 (a-phenylpropyl amine) [Ni NCS) u-phenylpropylamine) [Ni (NCS 2 u-phenylbutylamine) [Ni (NCS) 2 (u-phenylbutylamine) [Ni (NCS u-phenylamylamine) [Ni (NCS (a-phenylamy1amine) [Ni (NCS 2 a-phenylisoamylamine) [Ni(NCS a-phenylisoamylamine) [Ni (NCS a-phenylhexylamine [Ni (NCS ot-phenylhexylamine [Ni (NCS) 2 a-phenylisohexylamine) [Ni (NCS) (a-pheny1hept-ylamine) [Ni (NCS 2 (a-phenylheptylamine) [Ni (NCS) 2 ai-phenyloctylamine) [Ni (NCS) 2 u-phenyloctylamine) [Ni (NCS 2 a-phenylironylarnine) [Ni (NCS (a-pheny1nonylamine) [Ni (NCS 2 oc- (p-nonylphenyl) ethylamineh] 

1. A WERNER COMPLEX HAVING THE GENERAL FORMULA NI(SCN)2XN WHEREIN N IS AN EVEN NUMBER FROM 1 TO 5, X IS AN ALPHA-ARYLALKYLAMINE HAVING THE GENERAL FORMULA- 